 Stereochemistry - is a branch of chemistry which studies about the

three-dimensional arrangement of atoms (groups) in space.

 It is a branch of chemistry that focuses on the three-dimensional (3D)
arrangement of atoms in molecules and how this spatial arrangement
affects the chemical properties and reactivity of those molecules.
 Isomers are compounds that have the same molecular formula but
different arrangements of atoms or different spatial orientations,
which can lead to distinct physical and chemical properties.
 Isomers: different compounds with the same molecular formula.
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• Constitutional isomers (also called structural isomers) are
compounds that have the same molecular formula but differ in the
connectivity of their atoms—that is, the way the atoms are bonded to
each other.
• Because of differences in bonding, constitutional isomers have
different physical and chemical properties.
• Skeletal, positional and functional isomers.
• Stereoisomers are a type of isomer where molecules have the same
molecular formula and the same connectivity of atoms but differ in the
spatial arrangement of their atoms or groups.
• There are two main types of stereoisomers:
• Geometrical isomers (cis-trans isomers): it arises when atoms or
groups are arranged differently in space due to restricted rotation
of a bond or bonds in a molecule.
• The two main forms are:
:: Cis isomer: The substituent groups are on the same side of a
reference plane/ the two same groups are arranged on the same side
of a double bond.
:: Trans isomer: The substituent groups are on opposite sides of a
reference plane/ the two same groups are arranged on the opposite
side of a double bond.
• A common example is the isomers of alkenes, like cis-2-butene
and trans-2-butene, where the methyl groups (–CH₃) are on the
same side in cis and on opposite sides in trans.

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• Chiral isomers (enantiomers and diastereomers): These arise from
the presence of chirality in the molecule, which means there is a
carbon atom bonded to four different groups (a chiral center).
• Enantiomers: These are non-superimposable mirror images of each
other.
• They have identical physical properties except for how they interact
with polarized light and certain chiral substances.

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 Diastereomers: are a type of stereoisomer, which are molecules that
have the same molecular formula and the same connectivity of atoms,
but differ in the spatial arrangement of atoms or groups.
 Same constitution (connectivity) but differ in configuration at one or
more of the stereogenic centers./
 Non-superimposable, non-mirror image isomer
 Diastereomers exist in compounds that have more than one chiral
center.
 Diastereomers can have different physical properties (e.g., boiling
point, melting point, solubility) and different chemical reactivity,
despite having the same molecular formula.
 Chirality
1. Chiral molecule is one that is not identical with its mirror image.
• Non-superimposable with its mirror image
2. Achiral molecules that are identical with their mirror-images
• Superimposable with its mirror image

The mirror image of a left Left and right hands

hand is aright hand. are not superposable
(a) Three-dimensional drawings of the 2-butanol enantiomers I and II.
(b) Models of the 2-butanol enantiomers. (c) An unsuccessful attempt
to superpose models of I and II.
 Asymmetric Carbons, Chirality Centers, Stereogenic center and
Stereocenters
 A tetrahedral carbon atom bonded with four different groups

The tetrahedral carbon atom of 2-butanol that bears four different

Groups. [By convention such atoms are often designated with an asterisk (*)].

Identify the asymmetric carbons of the following compounds

1. 3-chloropentane 4. 2-methylbutane
2. 3-methylcyclohexane 5. 1,2-dichlorocyclobutane
3. 3,3-dimethylpentane 6. 2,3-dimethylhexane
 Isomers with One Asymmetric Carbon
• A compound with one asymmetric carbon, such as 2-bromobutane, can exist as two
different stereoisomers.

Although 2-butanol is a chiral molecule and therefore has two enantiomers (I & II), but 2-
propanol is achiral and does not exist as an enantiomeric pair. 2-Propanol has plane of
symmetry . 12
 Drawing Enantiomers
1. Perspective Formula
• Shows two of the bonds to the asymmetric carbon are in the plane of the paper, one
bond as a solid wedge indicating out of the paper, and the fourth bond as a hatched
wedge extending behind the paper.

2. Fischer Projection
• A Fischer projection represents an asymmetric carbon as the point of intersection of
two perpendicular lines; horizontal lines represent the bonds that project out of the
plane of the paper toward the viewer, and the vertical lines represent the bonds that
extend back from the plane of the paper away from the viewer.

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 R-S configuration

1. Each of the four groups attached to the stereocenter is assigned a priority

based on the atomic number of the atom that is directly attached to the
stereocenter.
The group with the lowest atomic number is given the lowest priority, 4; the
group with next higher atomic number is given the next higher priority, 3; and
so on.
• In the case of isotopes, the isotope of greatest atomic mass has highest priority.
2. Assign a priority at the first point of difference.
• When the atomic number of the atoms that are directly attached to the
stereocenter is the same, then the next set of atoms are examined.
 Orient the molecule so that the group (or atom) with the lowest priority (4) is directed away
from you.
 Then draw an imaginary arrow from the group (or atom) with the highest priority (1) to the
group (or atom) with the next highest priority (2).
 If the direction from highest priority (1) to the next highest (2) to the next (3) is clockwise,
the enantiomer is designated R.
 If the direction is counterclockwise, the enantiomer is designated S.
 Enantiomers have opposite configuration.
• If there are two substituents with equal rank, proceed along the two
substituent chains until there is a point of difference.

• If a chain is connected to the same kind of atom twice or three times, check to see if
the atom it is connected to has a greater atomic number than any of the atoms that
the competing chain is connected to.

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 Properties of Enantiomers
Enantiomers have same physical properties, e.g. melting points, boiling points and
solubilities.
They also have same chemical properties.
However, they differ in their activities with plane polarized light, which gives rise to
optical isomerism,
Enantiomers will rotate plane polarized light the same magnitude (α) but in
opposite directions (+ or -). and also in their pharmacological actions.

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 Optical isomerism
• Two molecules which are non-superimposibile mirror images of each other are called
enantiomers.
• One special property of enantiomers is that despite being distinct molecules,
enantiomers have the same physical properties.
• The only exception is that enantiomers will rotate plane polarized light in different
directions. This property is used to distinguish them.
• Since enantiomers are "handed" or "chiral", they can be distinguished by optical
activity
• This term refers to the property of chiral compounds (exclusively) of rotating the
plane of plane-polarized light to the right (clockwise) or to the left (counterclockwise).
• Plane-polarized light that passes through solutions of achiral compounds remains in
that plane ([a] = 0, optically inactive)

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• The two enantiomers have exactly the same ability to rotate this plane,
quantitatively, but they rotate it in opposite direction.
• Thus, if one enantiomer rotates the plane by 10.5 degrees clockwise
(considered a positive rotation), the other rotates it by -10.5 degrees (i.e., in
the counterclockwise direction).
• A positive (clockwise) rotation is sometimes called dextrorotation and a
negative rotation is sometimes called levorotation
• A polarimeter measures the rotation of plane-polarized light that has
passed through a solution
• Rotation, in degrees, is []

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• Specific rotation, []D for an optically active compound

 The specific rotation of the enantiomer is equal in magnitude but opposite in sign (+)-lactic
acid = +3.82; (-)-lactic acid = -3.82
Example:-
1. A 1.20 g sample of cocain [α]D =-16o was dissolved in 7.5 ml chloroform and placed in a
sample tube having a path length of 5.00 cm. what was the observed rotation? Is cocaine
dextrorotatory or levorotatory?
2. A 1.50 g sample of coniine, the toxic extract of poison hemlock, was dissolved in 10.0 mL of
ethanol and placed in a sample cell with a 5.00 cm path length. The observed rotation at
the sodium line was +1.21°.Calculate [α]D for coniine. Is coniine dextrorotatory or
levorotatory?
• A mixture of equal amounts of two enantiomers is called a racemic mixture or a
racemate.
• A racemic mixture is a 50:50 mixture of the 2 enantiomers of a chiral compound.
• Racemic mixtures do not rotate the plane of polarized light.
• They are optically inactive because for every molecule in a racemic mixture that
rotates the plane of polarization in one direction, there is a mirror-image molecule
that rotates the plane in the opposite direction.
• As a result, the light emerges from a racemic mixture with its plane of polarization
unchanged. The symbol (+-) is used to specify a racemic mixture. Thus, (+-)-2-
bromobutane indicates a mixture of (+)-2-bromobutane and an equal amount of
(-)-2-bromobutane.
• Separation of racemates into their component enantiomers is a process called
resolution.
• Since enantiomers have identical physical properties, such as solubility and
melting point, resolution is extremely difficult but diastereomers have different
physical properties, and this fact is used to achieve resolution of racemates.
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 Molecules with more than one Stereocenter
1. Diastereomers are exist in molecules that have more than one stereogenic (chiral)
center:
2. Diastereomers are stereoisomers that are non-superimposable and not mirror images
of each other.
3. Enatiomers are stereoisomers that are non-superimposable and mirror images of each
other.
4. Enatiomers must have opposite configurations at all stereogenic centers
5. Diastereomers must have opposite configurations at some (one or more) stereogenic
centers, but the same configurations at other stereogenic centers
 A compound can have a maximum of 2n stereoisomers, where n equals the number of
asymmetric carbons.
• For example, 3-chloro-2-butanol has two asymmetric carbons.
• Therefore, it can have as many as four (22 = 4) stereoisomers.
 Conformations of Alkane

• Conformation- Different arrangement of atoms resulting from bond rotation

• Staggered- A low energy conformation where the bonds on adjacent atoms bisect
each other (60o dihedral angle), maximizing the separation.
• It is most stable: all 6 C-H bonds are as far away as possible
• Eclipsed- A high energy conformation where the bonds on adjacent atoms are
aligned with each other (0o dihedral angle).
• It is least stable: all 6 C-H bonds are as close as possible to each other
Thank you

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 • Name the following aromatic compounds:

H2 OH
NH2
A. C CH3
B. C. Br Br
H3C

CH3 Br
Cl Cl
CH3 CH3
Cl F.
D. E.
CH3
Cl Cl CH3
CH3 CH2
H3C CH3 I.
CH3
H.
G.

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 What is the IUPAC name of the following compound?

OH OH OH
H2 H
A. H C C C C OH B. C. H2
3 CH3 CH3
H C

H3C C CH3
H

H3C F.
H2 H2 N CH3 OH
D. H3C C O C CH3 E. H3C
H3C
CH3
H2 H2
G. H3C N C C CH3
CH3 CH3 CH3 H2C CH3
H2 O O O
H2 H2 H
H. H3C C C C CH3 I. J. H3C C C C CH
H H3C C C C CH H H

CH3 CH3
CH3
K. O O
H2 H2 CH3 O
H
H3C C C C C C CH3 L. H2C C C OH
CH3
CH3 27